U.S. patent number 6,391,923 [Application Number 09/615,422] was granted by the patent office on 2002-05-21 for aqueous polymer dispersion, its preparation and use.
This patent grant is currently assigned to Clariant GmbH. Invention is credited to Hendrik Ahrens, Klaus Pollmann, Achim Stankowiak.
United States Patent |
6,391,923 |
Pollmann , et al. |
May 21, 2002 |
Aqueous polymer dispersion, its preparation and use
Abstract
The present invention relates to aqueous dispersions preparable
by polymerization of an olefinically unsaturated, water-insoluble
compound in the presence of a water-soluble allyl or vinyl ether of
the formula 1 ##STR1## in which b is 0 or 1 n is 0 or 1 k is an
integer from 1 to 20, X is O or N[(A--O).sub.m --R] A is C.sub.2
-C.sub.4 -alkylene m is an integer from 5 to 900, and R is H or
C.sub.1 -C.sub.4 -alkyl, and in which A is not exclusively C.sub.3
- or C.sub.4 -alkylene, by mixing the olefinically unsaturated
water-insoluble compound with the water-soluble allyl and vinyl
ether in water, and triggering the polymerization by a free-radical
initiator.
Inventors: |
Pollmann; Klaus (Burghausen,
DE), Ahrens; Hendrik (Osnabruck, DE),
Stankowiak; Achim (Altotting, DE) |
Assignee: |
Clariant GmbH (Frankfurt,
DE)
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Family
ID: |
26054154 |
Appl.
No.: |
09/615,422 |
Filed: |
July 13, 2000 |
Foreign Application Priority Data
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Jul 13, 1999 [DE] |
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199 32 572 |
Aug 19, 1999 [DE] |
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199 39 266 |
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Current U.S.
Class: |
514/714; 524/755;
526/310; 526/312; 526/332; 526/333 |
Current CPC
Class: |
C08F
2/30 (20130101); C08F 261/00 (20130101); C08F
261/06 (20130101); C08F 2/20 (20130101); C08F
290/06 (20130101); C08G 65/337 (20130101); C08F
255/00 (20130101); C08F 216/1433 (20200201); C08F
216/1458 (20130101); C08G 65/2624 (20130101); C08F
293/005 (20130101); C08F 216/1416 (20130101); C08G
65/2609 (20130101); C08F 287/00 (20130101) |
Current International
Class: |
C08F
293/00 (20060101); C08F 2/20 (20060101); C08F
2/12 (20060101); C08F 2/30 (20060101); C08G
65/00 (20060101); C08F 216/14 (20060101); C08F
261/00 (20060101); C08F 290/06 (20060101); C08G
65/337 (20060101); C08F 216/00 (20060101); C08G
65/26 (20060101); C08F 287/00 (20060101); C08F
290/00 (20060101); C08F 255/00 (20060101); C08F
261/06 (20060101); C08J 003/32 () |
Field of
Search: |
;526/332,333,312,310
;524/714,755 |
References Cited
[Referenced By]
U.S. Patent Documents
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5798425 |
August 1998 |
Albrecht et al. |
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Foreign Patent Documents
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0 736 553 |
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Oct 1996 |
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EP |
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0 870 784 |
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Oct 1998 |
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EP |
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5-209052 |
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Aug 1993 |
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JP |
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Other References
WP. J. Bailey in Chemistry and Technology of water soluble
Polymers, Plenum Press, 1983, p. 261-265..
|
Primary Examiner: Wu; David W.
Assistant Examiner: Cheung; William K.
Attorney, Agent or Firm: Silverman; Richard P.
Claims
What is claimed is:
1. An aqueous dispersion preparable by polymerization of an
olefinically unsaturated, water-insoluble compound in the presence
of a water-soluble allyl, or vinyl ether of the formula 1
##STR6##
in which
b is 0 or 1
n is 0 or 1
k is an integer from 1to 20,
X is O or N[(A--O ).sub.m --R]
A is C.sub.2 -C.sub.4 -alkylene
m is an integer from 5 to 900, and
R is H or C.sub.1 -C.sub.4 -alkyl,
and in which A is not exclusively C.sub.3 - or C.sub.4 -alkylene,
by mixing the olefinically unsaturated water-insoluble compound
with the water-soluble allyl or vinyl ether in water, and
triggering the polymerization by a free-radical initiator.
2. The aqueous dispersion as claimed in claim 1, in which k is a
number from 4 to 8.
3. The aqueous dispersion as claimed in claim 1, in which X is
oxygen.
4. The aqueous dispersion as claimed in claim 1, in which R is
hydrogen.
5. The aqueous dispersion as claimed in claim 1, in which A is
ethylene or propylene.
6. The aqueous dispersion as claimed in claim 1, in which
--(A--O).sub.m -- is an alkylene oxide block polymer of the formula
##STR7##
in which
a is a number from 0 to 300,
b is a number from 5 to 300,
c is a number from 0 to 300.
7. The aqueous dispersion as claimed in claim 1, in which
--(A--O).sub.m -- is an ethoxy chain having from 8 to 240 ethoxy
units.
8. The aqueous dispersion as claimed in claim 6, wherein
a is a number from 1 to 80,
b is a number from 8 to 80, and
c is a number from 1 to 80.
9. The aqueous dispersion as claimed in claim 6, wherein
a is a number from 2 to 35,
b is a number from 10 to 45, and
c is a number from 8 to 35.
Description
BACKGROUND OF THE INVENTION
The present invention relates to polymer dispersions which can be
prepared using polymerizable polyalkylene glycol macromonomers.
The polymeric emulsifiers and protective colloids used for very
diverse applications are generally ambivalent copolymers which
contain both hydrophobic and hydrophilic comonomer fractions. A
typical example is the partially hydrolyzed polyvinyl acetate used
in the suspension polymerization of, for example, styrene,
disclosed, for example, in W. P. J. Bailey in Chemistry and
Technology of water-soluble Polymers, Plenum Press, 1983 page 261
et seq., ISBN 0306-41251-9, which adsorbs via the nonhydrolyzed
fractions of vinyl acetate to the emulsified styrene droplets and,
via the hydrophilic fractions of polyvinyl alcohol, ensures
emulsification of these droplets in the aqueous suspension.
Copolymers of acrylic acid and hydrophobic acrylic and methacrylic
esters, such as, for example, dodecyl methacrylate, which are used
in the cosmetics sector to formulate and stabilize aqueous lotions
and emulsions of water-insoluble oils (lit: BF Goodrich product
information "Pemulen Emulsifiers" 1995), or acrylic copolymers,
which are used to stabilize aqueous dispersions of silicates,
gypsum, talc, clay and other minerals in the exploration of
petroleum and formulation of building materials (EP-A-0 870784),
act in a similar way.
DESCRIPTION OF THE RELATED ART
JP-A-5-209 052 discloses copolymers of vinyl chloride with vinyl
polyether macromonomers which are produced in the form of solid
products. A dispersing action of the vinyl polyether macromonomers
is not disclosed.
EP-A-0 736 553 discloses copolymers of carboxylic acids or
derivatives thereof and propoxylated vinyl ethers, but these too do
not form a dispersion.
SUMMARY OF THE INVENTION
The object of the present invention was to find a process with
which copolymers can be directly obtained as aqueous
dispersions.
The present invention describes a class of water-dispersed
copolymers which can be prepared by copolymerizing allyl or vinyl
polyethers with known, mostly hydrophobic monomers. The copolymers
can be used without a diluent for the emulsification/dispersion,
or, depending on the process and intended use, such as, for
example, in the case of emulsion polymerization, can be prepared in
situ by adding small amounts of the polymerizable
macromonomers.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention thus provides aqueous dispersions preparable by
polymerization of an olefinically unsaturated, water-insoluble
compound in the presence of a water-soluble allyl or vinyl ether of
the formula 1 ##STR2##
in which
b is 0 or 1
n is 0 or1
k is an integer from 1 to 20,
X is O or N[(A--O).sub.m --R]
A is C.sub.2 -C.sub.4 -alkylene
m is an integer from 5 to 900, and
R is H or C.sub.1 -C.sub.4 -alkyl,
and in which A is not exclusively C.sub.3 - or C.sub.4 -alkylene,
by mixing the olefinically unsaturated water-insoluble compound
with the water-soluble allyl or vinyl ether in water, and
triggering the polymerization by a free-radical initiator.
k preferably assumes values from 2 to 12, in particular 4 to 8. X
is preferably oxygen. R is preferably hydrogen. In a further
preferred embodiment n=1, b=0 and X=O.
In the alkoxy chain given by (A--O).sub.m, A is preferably an
ethylene or propylene radical, in particular an ethylene radical.
The total number of alkoxy units is preferably between 8 and 240,
in particular between 16 and 115. The alkoxy chain can be a block
polymer chain which has alternating blocks of different alkoxy
units, preferably ethoxy and propoxy units. It can also be a chain
with alkoxy units in random sequence.
In a preferred embodiment, --(A--O).sub.m -- is an alkoxy chain of
the formula ##STR3##
in which
a is a number from 0 to 300, preferably 1 to 80, in particular 2 to
35
b is a number from 5 to 300, preferably 8 to 80, in particular 10
to 45
c is a number from 0 to 300, preferably 8 to 80, in particular 8 to
35.
In a further preferred embodiment, --(A--O).sub.m -- is an ethoxy
radical having from 8 to 240 ethoxy units.
A common feature of all of the embodiments is that preferably at
least 50 mol % of the radicals (A--O) are ethoxy radicals, in
particular 60 to 90 mol % are ethoxy radicals. The number of
propoxy and butoxy radicals is, in a preferred embodiment, at most
so great that the cloud point of the compound of the formula 1 in
water is still at 30.degree. C. or above.
If X is N[(A--O).sub.m --R], then the compounds of the formula 1
have the following structure: ##STR4##
The compounds of the formula 2, in which k, A, m, n, b and R are as
defined above, are also provided by the invention.
The invention further provides compounds of the formula 1 in which
X=O and R=C.sub.1 -C.sub.4 -alkyl. Preferably, in such compounds
n=0.
The compounds of the formula 1 are also referred to below as
polymerizable macromonomers.
The preparation of the polymerizable macromonomers, and
illustrative applications of the dispersions according to the
invention are described in more detail below and illustrated by
reference to examples.
The polymerizable macromonomers are prepared by anion/alkali
initiated polymerization of hydroxy- or amino-functional allyl or
vinyl ethers (ethers which still have at least one active hydrogen
atom) with alkylene oxide or mixtures of alkylene oxides in random
distribution or as block copolymers. Furthermore, the resulting
macromonomers can also be etherified at the terminal hydroxyl
groups by means of a Williamson synthesis. The hydroxy- or
amino-functional allyl or vinyl ethers have formula 3 ##STR5##
where Y=OH, NH.sub.2.
The degree of water solubility, defined by the cloud point, of the
polymerizable macromonomers, and the extent of their
hydrophilicizing and dispersing action can be set by the ratio and
number of alkylene oxide units, preferably of ethylene oxide to
propylene oxide, and through the choice of the hydroxy- or
amino-functional allyl or vinyl ether.
The free-radical initiated copolymerization of the polymerizable
macromonomers with olefinically unsaturated water-insoluble
monomers produces the copolymer dispersions according to the
invention. Suitable water-insoluble monomers which can be
polymerized with the macromonomers are, for example, the
following:
vinyl monomers, such as carboxylic esters of vinyl alcohol, for
example vinyl acetate, vinyl propionate, vinyl ether of isononanoic
acid or of isodecanoic acid, styrene and stilbene,
olefinically unsaturated carboxylic esters, such as ethyl acrylate,
n-butyl acrylate, i-butyl acrylate, hexyl acrylate, 2-ethylhexyl
acrylate, hydroxyethyl acrylate, and the corresponding methacrylic
esters,
olefinically unsaturated carboxylic acids, such as acrylic acid,
methacrylic acid and itaconic acid and their sodium, potassium and
ammonium salts,
olefinically unsaturated sulfonic acids and phosphonic acids and
their alkali metal and ammonium salts, such as
acrylamidomethylpropanesulfonic acid (AMPS) and its alkali metal
and ammonium, alkylammonium and hydroxyalkylammonium salts,
allylsulfonic acid and its alkali metal and ammonium salts,
acryloyloxethylphosphonic acid and its ammonium and alkali metal
salts, and the corresponding methacrylic acid derivatives,
olefinically unsaturated amines, ammonium salts, nitriles and
amides, such as dimethylaminoethyl acrylate,
acryloyloxethyltrimethylammonium halides, acrylonitrile,
N-methacrylamide, N-ethylacrylamide, N-propylacrylamide, and the
corresponding methacrylic acid derivatives and
vinylmethylacetamide,
olefins, such as ethylene, propene and butenes, pentene,
3-butadiene and chloroprene,
vinyl halides, such as vinyl chloride, vinylidene chloride and
vinylidene fluoride.
The present invention further relates to the use of the
above-defined macromonomers of the formula 1 in emulsion
polymerizations or suspension polymerizations.
The invention further provides for the use of the polymerizable
polyalkylene macromonomers according to the invention as
emulsifiers or dispersants.
The compounds of the formula 1 can be used in suspension or
emulsion polymerizations alone as emulsifiers, and also in a
mixture with anionic and/or nonionic surfactants known in the prior
art.
Customary anionic surfactants are sodium alkyl sulfate, sodium
dodecylbenzenesulfonate, sodium alkylsulfonate, sodium and ammonium
alkylpolyethylene glycol ether sulfates, sodium and ammonium
alkylphenol polyethylene glycol ether sulfates, and
alkylpolyethylene glycol ether phosphoric mono-, di- and triesters
and mixtures thereof, and alkylphenol polyethylene glycol ether
phosphoric mono-, di- and triesters and mixtures thereof.
EXAMPLES
The examples below illustrate the invention in more detail.
Example 1
50.5 g of 4-hydroxybutyl vinyl ether were adjusted to a pH of 14
using 0.2 mol NaOCH.sub.3 solution, and reacted with 440 g of
ethylene oxide at superatmospheric pressure at 140.degree. C. for 8
h. The resulting product (macromonomer) was completely
water-soluble, i.e. the cloud point of the macromonomer in water is
above 100.degree. C. The OH number is 62.8 mg/KOH/g, corresponding
to a molecular weight of 894 g/mol. This corresponds to a
polyethylene oxide monobutyl vinyl ether having 18 units of
ethylene oxide per vinyl ether unit. Using .sup.1 H-NMR and by
determining the iodine number (21 g/100 g) it was possible to
detect the total receipt of vinyl units (polymerizable units) per
molecule.
Example 2
50.5 g of 4-hydroxybutyl vinyl ether were adjusted to a pH of 14
using 0.2 mol NaOCH.sub.3 solution and firstly reacted with 145 g
of propylene oxide at superatmospheric pressure at 140.degree. C.
for 6 h. 440 g of ethylene oxide were added to the reaction
product, and the mixture was likewise reacted at superatmospheric
pressure at 140.degree. C. for 8 h. The resulting product
(macromonomer) was still completely water-soluble at room
temperature, exhibited a cloud point in water of 64.4.degree.0 C.
and had surfactant, emulsifying properties. The OH number was 50.9
mg/KOH/g, corresponding to a molecular weight of 1100 g/mol. This
corresponds to a polyethylene oxide-polypropylene oxide block
copolymer monobutyl vinyl ether having 18 units of ethylene oxide
and 4 units of propylene oxide per vinyl ether unit. Using .sup.1
H-NMR and by determining the iodine number (21 g/100 g) it was
possible to detect the total receipt of vinyl units (polymerizable
units) per molecule.
Example 3
50.5 g of diethylene glycol monovinyl ether were adjusted to a pH
of 14 using 0.2 mol NaOCH.sub.3 solution, and reacted with 440 g of
ethylene oxide at superatmospheric pressure at 140.degree. C. for 8
h. The resulting product (macromonomer) was completely
water-soluble, i.e. the cloud point of the macromonomer in water is
above 100.degree. C.
Example 4
50.5 g of aminopropyl vinyl ether were, adjusted to a pH of 14
using 0.1 mol NaOCH.sub.3 solution, and reacted with 440 g of
ethylene oxide at superatmospheric pressure at 140.degree. C. for 8
h. The resulting product (macromonomer) was completely
water-soluble, i.e. the cloud point of the macromonomer in water is
above 100.degree. C.
Example 5
49.5 g of diethylene glycol monovinyl ether were adjusted to a pH
of 14 using 0.1 mol NaOCH.sub.3 solution, and reacted with 800 g of
ethylene oxide at superatmospheric pressure at 140.degree. C. for
10 h. The resulting product (macromonomer) was completely
water-soluble, i.e. the cloud point was above 100.degree. C. The OH
number was 28 mg/KOH/g, corresponding to a molecular weight of 2000
g/mol. Using .sup.1 H-NMR and by determining the iodine number (10
g/100 g) it was possible to detect the total receipt of vinyl units
(polymerizable units) per molecule.
Example 6
The macromonomer from Example 1 is copolymerized with AMPS.
Example 7
The macromonomer from Example 2 is used as coemulsifier in the
emulsion polymerization of vinyl acetate and vinyl isodecanoate.
The copolymer of vinyl acetate and vinyl isodecanoate and the
macromonomer from Example 2 which forms in situ has good
emulsion-stabilizing properties because of its ambivalent
structure.
360 ml of water are charged to a glass flask, and 6 g of
.RTM.Emulsogen EPA 073 (alkyl ether sulfate), 24 g of .RTM.Tylose H
200 YG4 (hydroxyethylcellulose), 6 g of borax, 2.6 g of acetic acid
(99% strength) and 92 g of a 1.17% strength potassium
peroxodisulfate solution and 170 g of a monomer emulsion, which
consists of 480 g of water, 6 g of Emulsogen EPA 073, 17 g of
Emulsogen EPN 287 (alkyl ethoxylate), 30 g of the macromonomer
from, Example 2, 300 g of vinyl isodecanoate and 900 g of vinyl
acetate, are added. The mixture is then heated up to 76.degree. C.
and, after the reaction has started at 80.degree. C., the remaining
monomer emulsion and a further 210 g of a 1.17% strength ,potassium
peroxodisulfate solution are metered in over 3 hours. The mixture
is then stirred for 2 hours for after polymerization at 80.degree.
C. and cooled to room temperature. During the cooling phase, 3 g of
preservative (200 Mergal K9N) are added.
Example 8
The macromonomer from Example 2 is used as coemulsifier in the
emulsion polymerization of n-butyl acrylate, methyl methacrylate
and methacrylic acid. The copolymer of n-butyl acrylate, methyl
methacrylate and methacrylic acid and the macromonomer from Example
2 which forms in situ has good emulsion-stabilizing properties on
the basis of its ambivalent structure.
520 ml of water are charged to a glass flask, and 16 g of
.RTM.Emulsogen EPA 1954 (sodium alkyl sulfate), 15 g of a 3.75%
strength ammonium peroxodisulfate solution, 11.8 g of n-butyl
acrylate, 11.8 g of methyl methacrylate and 0.48 g of methacrylic
acid are added, and the mixture is stirred. The emulsion is heated
to 80.degree. C. with stirring and a monomer emulsion, which
consists of 475 ml of water, 16 g of Emulsogen EPA 1954, 4.8 g of
the macromonomer from Example 2, 440 g of n-butyl acrylate, 440 g
of methyl methacrylate, 8.8 g of methacrylic acid and 2.85 g of
ammonium peroxodisulfate is metered in over 4 hours. When all of
the monomer emulsion has been metered in and following an
afterpolymerization of one hour at 80.degree. C., the polymer
dispersion is cooled to room temperature and adjusted to pH 8-9
using ammonia solution.
Example 9
The macromonomer consisting of a block polymer of allyl alcohol,
Which has been reacted firstly with 5 mol of propylene oxide and
then with 30 mol of ethylene oxide, is used as coemulsifier in the
emulsion polymerization of n-butyl acrylate, methyl methacrylate
and methacrylic acid. The copolymer of n-butyl acrylate, methyl
methacrylate and methacrylic acid and the described allyl alkoxide
which forms in situ has good emulsion-stabilizing properties on the
basis of its ambivalent structure.
520 ml of water are charged to a glass flask, and 16 g of
.RTM.Emulsogen EPA 1954 (sodium alkyl sulfate), 15 g of a 3.75%
strength ammonium peroxodisulfate solution, 11.8 g of n-butyl
acrylate, 11.8 g of methyl methacrylate and 0.48 g of methacrylic
acid are added, and the mixture is stirred. The emulsion is heated
to 80.degree. C. with stirring, and a monomer emulsion which
consists of 460 ml of water, 32 g of Emulsogen EPA 1954, 4.8 g of
the described allyl alkoxylate, 440 g of n-butyl acrylate, 440 g of
methyl methacrylate, 8.8 g of methacrylic acid and 2.85 g of
ammonium peroxodisulfate, is metered in over 4 hours. When all of
the monomer emulsion has been metered in and following an
afterpolymerization of one hour at 80.degree. C., the polymer
dispersion is cooled to room temperature and adjusted to pH 8-9
using ammonia solution.
Example 10
To 100 g of the product from Example 1 are added, under nitrogen,
firstly 10 g of solid NaOH, and then 14 g of n-butyl chloride are
metered in. The reaction vessel is stirred at superatmospheric
pressure for 5 hours at 80.degree. C. The vessel is then evacuated
and heated under reduced pressure to 120.degree. C. and stirred for
a further 3 hours.
After the reaction mixture has cooled, it is repeatedly stirred
with 500 ml of water and left to stand to enable the phases to
separate. The aqueous sodium-chloride-containing phase is discarded
in each case. The upper phase (yield: 94 g/88%) is, according to
.sup.1 H-NMR, iodine number determination (24 g/100 g) and OH
number measurement (5 mg/g), finally the mono-n-butylpolyethylene
glycol mono-4-hydroxyvinyl ether having 18 units of ethylene
oxide.
Example 11
To 100 g of the product from Example 1 are added, under nitrogen in
an autoclave, firstly 10 g of solid NaOH, and then 7 g of methyl
chloride are metered in under superatmospheric pressure. The
reaction vessel is stirred at superatmospheric pressure for 5 hours
at 80.degree. C. The vessel is then evacuated and heated under
reduced pressure to 120.degree. C. and stirred for a further 3
hours.
After the reaction mixture has cooled, it is repeatedly stirred
with 500 ml of water and left to stand to enable the phases to
separate. The aqueous sodium-chloride-containing phase is discarded
in each case. The upper phase (yield: 92 g/90%) is, according to
.sup.1 H-NMR, iodine number determination (26 g/100 g) and OH
number measurement (5 mg/g), finally the mono-methyl polyethylene
glycol mono4-hydroxyvinyl ether having 18 units of ethylene
oxide.
* * * * *